Composition comprising ethyl cellulose and a fatty oil acid modified alkyd resin



, or maleic anhydrlde.

I atented Apr. 22, 19 52 COMPOSITION COMPRISING ETHYL CELLU- LOSE AND A FATTY OIL ACID MODIFIED ALKYD RE SIN Harry Burrell, Milburn, and Percy M. Clark,

Roselle, N. J., assignors to Interchemical Corporation, New York, N. Y., a corporation of Ohio N Drawing. Application April 22, 1949, Serial No. 89,144

I 1 This invention relates to new and useful compositions of matter. More particularly the invention relates to protective and decorative lacquer compositions containing ethyl cellulose and a drying oil modified alkyd resin.

Organic solvent soluble ethyl cellulose, i. e. ethyl cellulose of 43.5 to 49.5% ethoxyl content,

has been used extensively in the past in preparation of protective and decorative finishing compositions. It has been used either alone or with other film-forming materials in formulating a large variety of protective and decorative finishes. Ethyl cellulose lacquers dry to tough films which have good resistance to both alkali and acid, they have good aging properties and good color stability in sunlight. Notwithstanding the above valuable properties, ethyl cellulose lacquers have not been entirely satisfactory in many applications, especially where good adhesion to metal or other surfaces is required. To overcome the relatively poor adhesion of ethyl cellulose films; attempts have been made to mix the ethyl cellulose with a large variety of other film-forming materials, especially alkyd resins. So far the attempts to produce compatible mixtures of ethyl cellulose with fatty oil acid modified alkyd resins have not been very successful. It has been especially difficult to obtain "compatibility of short to medium length fatty oil acid modified alkyds and ethyl cellulose, particularly in mixtures containing high ratios of alkyd to ethyl cellulose.

We have now discovered that certain fatty oil acid modified alkyd resins are compatible with organic solvent soluble ethyl cellulose in all proportions. Based on this discovery we are able to formulate lacquer compositions containing ethyl cellulose and an alkyd resin in any desired ratio.

The fatty oil acid modified alkyd resins used prepared from fatty oil acid, alkyd resin-forming polyhydric alcohol, and polycarboxylic acid reactants resulting from the condensation or approximately 1 to 2 moles of dicyclopentadiene with l mole of ethylenically unsaturated dicarboxylic acid or anhydride such as funiaric acid The preparation of alkyd resins of this type is broadly disclosed and claimed in the copending application of. Charles S. Rowland and Albert G. Chenicek, Serial vNo. 764,576, filed July 29, 1947, now abandoned.

For the purposes of the present invention the .modi'fled alkyds are prepared by first condensing,

l mole of the unsaturated dicarboxylic acid, in

in the invention are those of 30 to 55% fatty oil acid length and acid numbers of about 20 to 80,

hydric alcohols in general.

10 Claims. (01. 260-46 2 h the presence orrabsence of the fatty oil acid. The condensation is preferably continued until condensation is complete as indicated by no further refluxing of the dicyclopentadiene. Polyhydric alcohol is then added, preferably in excess of the amount required to ester-ify .allthe carboxyl groups of the unsaturated dicarboxylic acid and the fatty oil acid, and heating at esterification temperatures is continued until the acid number is of the order of 20 to 80. When the fatty acid is not present during the condensation between dicyclopentadiene and unsaturated dicarboxylic acid, it is added preferably at the same time as the polyhydric alcohol or at any time during or after the addition of the polyhydric al-- cohol. In certain instances the polyhydric alcohol can be used in substantially stoichiometric quantities, for instance, with glycerol, and also in certain cases it can be used in excessto the extent of 40% or more, "especially with glycerol. It has been found however that the preferred range is from 10 to about 25% in excess of the amount required to combine with all of the carboxyl groups.

Alkyd resin-forming polyhydric alcohols which are operable in preparing the modified alkyd resins used in the present invention include trihydric alcohols such as glycerol and trimethylol propane, tetra-hydric alcohols such as erythr itol, and pentaerythritol, and hexahydric alcohols such as mannitol and sorbitol. It will be seen that these alcohols are those which are conventionally used in preparing alkyd resins and our numerous experiments indicate that the invention is operable with alkyd resin-forming poly- The term alkyd resin -forming polyhydric alcohol as used herein is meant to include polyhydric compounds which are conventionally used in the manufacture of alkyds, and which, as those persons skilled in the art are cognizant of, do not contain all sorts of reactive substituents which alter the course of the alkyd resin-forming reaction. Such subare alkyd resin-forming polyhydric alcohols, are

ingeneral, polyhydric alcohols containing from three to about ten hydroxyl groups, and containing no other substituent groups that are reactive under the conditions used in preparing alkyd resins. A minor amount of dihydric alcohols can be used along with the higher polyfunctional alcohols if desired.

The fatty acids that are operable in the present invention are those which are derived from drying oils, semi-drying oils and non-drying oils by aponification. Typical of the acids are: soya 'fatty acids, linseed fatty acids, castor oil fatty acids, dehydrated castor oil fatty acids, tall oil acids, oiticica oil acids, tung oil acids, cottonseed oil acids, and the like.

Ethyl cellulose having from about 43.5 to 49.5% ethoxyl content can be employed in the invention. It is well known that the solubility of ethyl cellulose in volatile organic solvents varies considerably, depending for the most part on the ethoxyl content, and to a lesser extent on the degree of polymerization or viscosity grade. Ethyl cellulose having an ethoxyl content of 46.5 to 48.5% is known to be more generally soluble the ratio by weight of ethyl cellulose to alkyd resin should be to 90 parts of ethyl cellulose to 90 to 10 parts of alkyd. Lacquers in which the film-forming materials are present within these limit can be formulated to give very resistant baked films having good adherence to metal surfaces. The adhesion of the films to metal surfaces increases with increasing amounts of alkyd resin in the film.

Another important feature of the invention is the fact that it makes possible the use of ethyl cellulose and alkyd resins in conjunction with other thermosetting and thermoplastic filmforming materials such as thermosetting melain volatile organic solvents than other ethyl cell5 mine-formaldehyde, urea-formaldehyde, and lulose grades and for this reason it will genphenol-formaldehyde resins, or thermoplastic erally be preferred in the present invention. materials such as acrylic resins, ester gums, and Such ethyl celluloses are generally soluble in one the like. Thermosetting resins, among other or more of the common organic solvents such as things, greatly improve the hardness and mar .ethyl acetate, butyl acetate, toluene, xylene, resistance of the films. 7 -benzene, acetone, methanol, ethanol, butanol, Lacquer compositions prepared in accordance ethylene dichloride, carbon tetrachloride, aliwith the invention also can contain other conphatic hydrocarbons, and the like or in mixtures ventional additives used in the formulation of :of these solvents. Other ethyl celluloses, for expaints, lacquers, varnishes and the like. For in- ..9,mp1e, thyl cellulose containing 43.5 to 45% 5 stance, catalysts or driers, used to increase the ;,ethoxyl, can be used in the invention but of course rate of cure of the films, may be employed. Also, more care must be used in selecting the solvent plasti iz r for the ethyl cellulose alkyd to be used. This however is not a serious handiresin can be used. capsince it is well known that the solubility of The following exa p in wh h the p r re .-.e,thyl cellulose in non-polar solvents such as hyby weigh are v n o f rther illustrate the indrocarbons generally decreases as the ethoxyl vention: cqment declleasesf Thus when the lower m" Example 1--Preparatz'on of the alkyd resins -tion derivat ves of cellulose are used, increasing amounts of polar solvent such as ethyl acetate, T0 592 P of dicyclopsntadiene, in a .methanol, ethylene dichloride, and the like, must 111011 flask equlpped Wlth stlrrer and reflux used denser, was added 444 parts of maleic anhydride The ratio of cellulose to resin parts of soy acids. This reaction in the lacquer is not critical, in fact, this is one mlxtllre was stirred and heated, Over a Pe of ofthedesirable characteristics of the lacquers 30 f 110 a p ra re f 1 C- A prepa redin accordance t theinvent1on since 4 exothermic reaction occurred at about 180 C. thealkyd resin and ethyl celluloses are compati- Whlch caused the temperature to rise p y v.ble in substantially all proportions, the propand au d rapid refluxing even thou erties of lacquer made in accordance with the the heel? o e was emoved- When the tem- I, invention can be varied over a broad range to suit Denture had again pp heating the particular application for which the lacquer 45 was continued for 50 minutes at 190-200 C. at is to be employed. It is obvious however that if which time refluxing had practically ceased. The j the modifying effect of the alkyd resin is to be reflux condenser was then removed and a curappreciable the alkyd must be used in an apprerent of inert gas (carbon dioxide) was started ciable amount. It has been our experience that: through the apparatus. Glycerol (400 parts) .TABLE I Ml R t' Fatty Acid Percent or i cyc io A m Resin No. and Alcohol pentadiene mess c 1 Reactants Fat-W to Malelc Pmyhydm Acid Anhydnde Alcohol 1 LinseedacidsPen- 45 l 10 39 taerythritol. Sameasl 45 1. s4 10 38 Same as l V 52 l 13 34 Linseed oil acids 54 1 l0 l2 Glycerol. 1:1 Mixture ofLin- 43 1 10 28 seed tung oil acids Glycerol. Same as 5 52 1 l0 l9 Soya acids Glyc- 30 1 10 '38 erol. Same as7 35 1 10 a2 Same as 7 40 l 10 31 Same as 7 50 1 10 31 Dehydrated cas- 1 10 44 tor oil acids Glycerol. Coconut oil acids l 0 68 Glycerol. Castor oil acids 50 1 0 37 Glycerol. Same as 4 52 1 l0 l4 Same as7 30 1 10 32 Dehydrated cas- 41 l 10 30 torloilacids Glyc- BIO s V was then added and heating was continued at 200 to 210 C. until the product had an acid number of 41 (2.5 hours was required). Numerous other resins have been prepared in similar manner except that when pentaerythritol was used as the polyhydric alcohol it was found preferable to add one-half of the required amount of pentaerythritol first, wait until the reaction had subsided, and then add the other half of the pentaerythritol. Table I lists several of the resins that have been prepared and found to be useful in the present invention. All the resins in Table I were made using maleic anhydride a the unsaturated dibasic acid reactant. In the preparation of lacquers the films dry faster if the ethyl cellulose content is about 25% or more of the total solids, in which case the films usually dry out of dust in less than 1-0 minutes and dry t'ack free in one half to one hour. The films are tough, fairly hard, and have good adhesion and gloss.

Example 2 A typical lacquer formulation according to the invention is as follows:

Resin No. 7 of Table I 15.0 Ethyl cellulose (46.8 to 48.5% ethoxyl, viscosity of approx. 7 cps. in 5% solution of of 80:20 toluol:eth'yl alcohol mixture at 25 0.) r 15.0 Toluene =-----lessees a l -la l l 28.0 Xylene r 24.5

When one coat of this lacquer was sprayed on bare wood, it dried dust free in minutes and dried tack-free in minutes. The dried film was cleanand free from orange peel or pebbled surface appearance.

Example 3 Resin No. 14 of Table I 10 Ethyl cellulose (same as Example 2) l 10 Toluene 51 Xylene -l 16 Ethyl alcohol, denatured 13 Em-ample 4 Resin No. 15 of Table I l- 1.7 Ethyl cellulose (same as Examp 15.0 T011101 i-i-u-L-H----L-' LZ-L' l----.;- ai 'G--- X57101 -..Icahn-s..1 -s a al 69.0 Ethyl alcohol, denatured 11.8

The above ingredients, when mixed, gave a clearlacquer. When the lacquer was coated on a glass panel it dried to a tack-free film in 10 min utes. The dried films were hard and tough, and had markedly better adhesion than straight ethyl cellulose films.

Eamnple 5 Resin No. 5 of Table I a 6.0 Ethyl cellulose (same as Example 2) 18.0 Toluol 1-5. 57.6 Xylol l 4.0 Ethyl alcohol, denatured- -1". ..l l 14.4

Films of the above lacquer dried tack-free in 7 minutes. Adhesion was improved by baking the i'llms at 300 F. for 15 minutes.

Example 6 Resin No. 16 of Table I 1-; 510 Ethyl cellulose (same as Example2) 15.0 Toluol 51.0 Xylol 6.0 Ethyl alcohol, denatured 13.0 n-Butanol 10.0

The above mixture gave a clear solution and produced extremely hard films with good adhesion when poured on glass panels. Taclhfree films were obtained after a 30 minute air dry.

Example 7 Resin No. 3 of Table I 1. 1- -l- 6.5 Ethyl cellulose '(same as Example 17.5 Toluol ..1 l- -1-11 11. 55.5 xylol .1 6.5 Ethyl alcohol, denatured 1-1-1- -..1 14.0

This lacquer gave clear tough films with good adhesion. The films became tack tree after drying in air for 11 minutes.

Example 8 Resin No. 11 of Table I 10.0 Ethyl cellulose (44.5 to 45.5% ethoxyl content, and viscosity of approx. 50 cps in 5% solution in 70:30 toluolzetha'nol mix- The above ingredients ga e a clear lacquer which dried to tough rubbery films on air drying. Example 9 Resin No. llof Table I 10.0

Ethyl cellulose (45.5 to 46.8% ethoxyl content, and viscosity of approx. 22 cps. in 5% solution 70:30 toluol: ethanol mixture at 25 'C.) 10.0 Toluol v -l 1 48.0 Xylol -1 6.5 Ethyl alcohol, denatured 20.5 n-Butanol 5.0

The clear solution obtained from the above ingredients gave clear tough films having good adhesion.

This lacquer gave a tough, hard film. having only a faint trace of a haze.

Edldmpl 11 ResinNo. 11 from Table 'I 4.4a- 21.0 Ethyl cellulose (same as Example 2)-, 2.5

Butylated urea-formaldehyde. as 60% solu-' tion in an equal admixture of n-butanol and xylol, e. g. Uformite F-ZOO E 13.7 (solids basis) n-Butanol (including that added with the urea-for aldehyde resin) -8.3 Xylol (including that added with the ureaform'aldehyde resin) 41.4 Ethyl alcohol, denatured l 3.1 Toluol --'--a 8.3

n-Butyl acid phosphate (catalyst)....... 0.8

,tough films havingexcellent gloss.

The above mixture gave a slightly hazy solution typical of urea resin mixtures. Films of the lacquer can be baked at 150 F. for 1 hour to give hard, bright, mar resistant films havin ex cellent adhesion properties.

Example 12 A blue enamel was prepared by grinding Titanium dioxide 2.40 Iron blue 1.15 Iron oxide .90 Carbon black .35 Xylol 8.60 .Resin No. from Table I 3.60

in a steel ball mill for 72 hours and then adding this pigment dispersion to a vehicle consisting of The enamel was thinned to spraying viscosity with a thinner consisting of 30% xylol, 35% toluol, 20% ethyl alcohol and n-butanol. Sprayed coatings of the enamel air dried to glossy, moderately tough films, free from haze or signs of incompatibility. Harder and tougher enamels can be obtained by increasing the ratio of ethyl cellulose to resin to 50:50.

Example 13 A white enamel was prepared by mixing Titanium dioxide 12.5 Ethyl cellulose (45.8 to 48.5% ethoxyl and viscosity of approx. 22 cps. in 5% solution in 80:20 toluolzethanol mixture) 1.8 Ethyl alcohol, denatured 2.1 h Toluol 8.6

in a heavy dough mixer until the pigment was suitably dispersed. The pasty pigment dispersion was then added to a vehicle consisting of Ethyl cellulose (same as Example 2) 11.4 -Resin No. 3 from Table I 4.4 Xylol 20.0 Toluol 18.2 Ethyl alcohol, denatured 9.1 n-Butanol 11.9

Films of the enamel air dried quickly to hard,

Baking at 150 F. for 1 hour, or at 300 F. for 15 minutes, increased the hardness of the films. The films had good adhesion to Bonderized steel as well as to primec'oated steel.

Conventional driers, such as lead, cobalt and manganese driers, can be added to the above composition to increase the rate of cure of the We claim: 1. A resin composition comprising 10 to 90 parts ethyl cellulose having an ethoxyl content of 43.5to 49.5% admixed with 90 to 10 parts of a 30 to 55% fatty oil acid modified alkyd resin, said alkyd resin consisting of the heat Qsterification product of fatty oil acid, alkyd resin-forming polyhydric alcohol and polycarboxylic acid resulting from the condensation of 1 to 2 moles of dicyclopentadiene with 1 mole of alpha, betaethylenically unsaturated dicarboxylic acid.

2. A resin composition comprising 10 to parts ethyl cellulose having an ethoxyl content of 43.5 to 49.5% admixed with a plasticizer and 90 to 10 parts of a 30 to 55% fatty oil acid modified alkyd resin, said alkyd resin consisting of the heat esterification product of fatty oil acid, alkyd resin-forming polyhydric alcohol and polycarboxylic acid resulting from the condensation of 1 to 2 moles of dicyclopentadiene with 1 mole of alpha, beta-ethylenically unsaturated dicarboxylic acid.

3. A composition as claimed in claim 1 wherein the fatty oil acid is a drying oil fatty acid.

4. A composition of matter comprising a solution of 10 to 90 parts ethyl cellulose having an ethoxyl content of 43.5 to 49.5% and 90 to 10 parts of a 30 to 55% fatty oil acid modified alkyd resin, said alkyd resin consisting of the heat esterification product of fatty oil acid, alkyd resin-forming polyhydric alcohol and polycarboxylic acid resulting from the condensation of 1 to 2 moles of dicyclopentadiene with 1 mole of alpha, beta-ethylenically unsaturated dicarboxylic acid.

5. A composition of matter comprising a solu tion of 10 to 90 parts ethyl cellulose having an ethoxyl content of 43.5 to 49.5%, a plasticizer, and 9-0 to 10 parts of a 30 to 55% fatty oil acid modified alkyd resin, said alkyd resin consisting of the heat esteriiication product of fatty oil acid, alkyd resin-forming polyhydric alcohol, and polycarboxylic acid resulting from the condensation of l to 2 moles of dicyclopentadiene with 1 mole of alpha, beta-ethylenically unsaturated dicarboxylic acid.

6. A composition of matter comprising a solution of 10 to 90 parts ethyl cellulose having an ethoxyl content of 43.5 to 49.5%, a thermosetting resin of the group consisting of thermosetting urea-formaldehyde resin, melamine-formaldehyde resin and phenol-formaldehyde resin, and 90 to 10 parts of a 30 to 55% fatty oil acid modified alkyd resin, said alkyd resin consisting of the heat esterification product of fatty oil acid, alkyd resin-forming polyhydric alcohol, and polycarboxylic acid resulting from the condensation of 1 to 2 moles of dicyclopentadiene with 1 mole alpha, beta-ethylenically unsaturated dicarboxylic acid.

7. A composition as claimed in claim 4 wherein the fatty oil acid is a drying oil fatty acid.

8. A composition as claimed in claim 4 wherein the polyhydric alcohol is glycerol.

9. A composition as claimed in claim 4 wherein the polyhydric alcohol is pentaerythritol.

10. A composition as claimed in claim4 wherein the polycarboxylic acid reactant is maleic an hydride.

HARRY BURRELL. PERCY M. CLARK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,243,185 Bacon et a1 May 27, 1941 2,290,563 Kauppi July 21, 1942 2,423,234 Gerhart et a1 July 1, 1947 

1. A RESIN COMPOSITION COMPRISING 10 TO 90 PARTS ETHYL CELLULOSE HAVING AN ETHOXYL CONTENT OF 43.5 TO 49.5% ADMIXED WITH 90 TO 10 PARTS OF A 30 TO 55% FATTY OIL ACID MODIFIED ALKYD RESIN, SAID ALKYD RESIN CONSISTING OF THE HEAT ESTERIFICATION PRODUCT OF FATTY OIL ACID, ALKYD RESIN-FORMING POLYHYDRIC ALCOHOL AND POLYCARBOXYLIC ACID RESULTING FROM THE CONDENSATION OF 1 TO 2 MOLES OF DICYCLOPENTADIENE WITH 1 MOLE OF ALPHA BETAETHYLENICALLY UNSATURATED DICARBOXYLIC ACID. 